Molding compositions comprised of polyimide/N-vinylpyrrolidone prepolymer and epoxy resin

ABSTRACT

Novel thermosetting compositions, including a polyimide/N-vinylpyrrolidone prepolymer, optionally comprising an unsaturated polyester, and an epoxy resin, are well adapted for the molding of a variety of useful shaped articles.

This application is a division of application Ser. No. 87,650, filedOct. 23, 1979 now U.S. Pat. No. 4,316,002.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel thermosetting compositionscomprising certain imido prepolymers and an epoxy resin.

2. Description of the Prior Art

Thermosetting compositions comprising a bis-maleimide andN-vinyl-2-pyrrolidone are already known to this art; Belgian Pat. No.846,365 (U.S. Pat. No. 4,111,919). Such compositions may be used in theprepolymer state for molding operations, either by casting orimpregnation. Further, improvements in the properties of epoxy resinstoo are known to have been sought, by combining same with thederivatives of a polyimide of an unsaturated carboxylic acid. Comparethe compositions described in, for example, French Pat. Nos. 2,045,087and 2,076,447. The '087 French patent has for a major object thehardening or curing of epoxy resins by means of a prepolymer obtained byheating a bis-imide and a polyamine. The '447 French patent mentions thecombination of an epoxy resin, a bis-imide and a carboxylic acidanhydride which, after hardening, yields materials having increasedmechanical properties.

However, for certain applications it would be useful to providecompositions simultaneously having good stability at ambienttemperature, greater fluidity at low temperatures than the imideprepolymers and adapted for the ultimate preparation of materials havingexcellent mechanical properties.

SUMMARY OF THE INVENTION

Accordingly, a major object of the present invention is the provision ofsuch stable, more fluid and stronger compositions, the same comprising:

[i] a prepolymer obtained by reacting:

(a) a polyimide having the structural formula: ##STR1## wherein Drepresents ##STR2## wherein Y represents H, CH₃ or Cl and m is equal to0, 1 or 2, R represents an organic radical of valence n, containing from2 to 50 carbon atoms, and n represents a number having an average valuebetween 2 and 5; with

(b) N-vinyl-2-pyrrolidone; and

(c) optionally, with an unsaturated polyester;

[ii] an epoxy resin; and,

[iii] a hardener or curing catalyst for the epoxy resin.

DETAILED DESCRIPTION OF THE INVENTION

More particularly, according to the invention, the polyimide preferablyis a bis-imide having the structural formula: ##STR3## wherein thesymbol L represents a divalent radical selected from the groupcomprising cyclohexylene, phenylene radials and radicals having thestructural formula: ##STR4## wherein T represents --CH₂ --, --C(CH₃)₂--, --O-- or SO₂.

Among the bis-maleimides corresponding to the formulae and definitionsgiven hereinabove, most preferred isN,N',4,4'-diphenylmethane-bis-maleimide.

The polymides (a) are known to the art. Same may be prepared by themethods disclosed in U.S. Pat. No. 3,018,290 and British specificationNo. 1,137,592.

The polyimide and the N-vinyl-2-pyrrolidone-2 are employed in quantitiessuch that, if n₁ designates the number of carbon-carbon double bondsintroduced by the polyimide and n₂ the number of --CH═CH₂ groupscontributed by the N-vinyl-2-pyrrolidone, the ratio of n₁ /n₂ is between1.01 and 10.

The unsaturated polyesters that are optionally coreacted are themselveswell known to the art. Same are typically prepared by polycondensationof at least one polycarboxylic acid or ester-forming derivatives thereof(hereafter the "polycarboxylic derivatives") and at least one polyol, atleast one of which contains olefinic unsaturation; the term"polycarboxylic derivatives" is to be understood as connoting the freeacids, the esters of lower alcohols, the acid chlorides and possibly theanhydrides. In the compositions according to the invention, mostsuitable are the polyesters prepared from starting unsaturated monomersof diacid or dianhydride type having an α,β-site of olefinicunsaturation.

Exemplary of such dicarboxylic derivatives are the maleic, chloromaleic,itaconic, citraconic, aconitic, pyrocinchonic, fumaric, chlorendic,endomethylenetetrahydrophthalic, tetrahydrophthalic, ethylmaleic,succinic, sebacic, phthalic, isophthalic, adipic and hexahydrophthalic.Among the polyols, the most common are ethylene glycol, propyleneglycol, diethylene glycol, triethylene glycol, neopentyl glycol,tetraethylene glycol, butylene glycol, dipropylene glycol, glycerol,trimethylol propane, pentaerthrytol, sorbitol,bis(hydroxymethyl)-3,3-cyclohexane, tris(β-hydroxymethyl) isoycanurate.

The preparation of the unsaturated polyesters may be effected utilizingknown methods (see, for example, Kirk Othmer, Encyclopedia of ChemicalTechnology, 2nd edition, Vol. 20). The molecular weight of suchconventional polyesters is typically between 1000 and 10,000.

The expression "unsaturated polyester" as utilized herein is intended toconnote both the aforedescribed polycondensates and solutions of saidpolycondensates in polymerizable olefinically unsaturated, monomers. Thepolymerizable liquid monomers may be, for example, hydrocarbons(styrene, vinyl toluene, divinyl benzene), ethers (vinyl oxide andchloro-2-ethyl oxide), derivatives of acrylic acid or methacrylic acid,and allyl derivatives.

The N-vinylpyrrolidone is itself a known monomer solvent for theunsaturated polyesters. It should, therefore, be understood that, if anunsaturated polyester is used, it may naturally be in the form of asolution in a polymerizable monomer, in view of the fact that thepolymers according to the invention must always be prepared fromN-vinylpyrrolidone. When used, the polymerizable monomer may comprisefrom 10 to 60% by weight of the solution of the unsaturated polyester.In the compositions according to the invention, the weight of thepolyester or of the aforedefined solution preferably comprises from 5 to60% of the total weight of the combination ofpolyimide+N-vinylpyrrolidone. The preparation of the prepolymers fromthe polyimide, N-vinylpyrrolidone and, optionally, the unsaturatedpolyester, is described in Belgian Pat. No. 846,365.

The prepolymer [i] defined hereinabove preferably has a softening pointbetween 30° and 150° C.

The second component [ii] of the compositions according to the inventionis an epoxy resin. The expression "epoxy resin" is intended herein inits conventional sense, i.e., as reflecting a molecule comprising aplurality of ##STR5## groups, each susceptible to cross-linking. All ofthe typical epoxy resins are intended. Among same, the following arerepresentative: glycidyl ethers obtained by reacting, in known manner,epichlorohydrin with polyols such as gycerol, trimethylolpropane,butanediol or pentaerythritol. Other suitable epoxy resins are theglycidyl ethers of phenols, such as bis(4-hydroxyphenyl)-2,2-propane,bis(hydroxyphenyl)methane, resorcinol, hydroquinone, pyrocatechol,phloroglucinol, 4,4'-dihydroxydiphenyl, and the condensation products ofphenol/aldehyde type. It is also envisaged to utilize the products ofthe reaction of epichlorohydrin with primary or secondary amines such asbis(4-methylaminophenyl)methane or bis(4-aminophenyl)sulfone, togetherwith aliphatic or alicyclic polyepoxides prepared by epoxidation, bymeans of peracids or hydroperoxides, of the corresponding unsaturatedspecies. These different types of resins are well described in theliterature and for their preparation, see, for example, the work ofHouben-Weil, Vol. 14/2, page 462.

Particularly suitable epoxy resins are the glycidyl ethers ofpoly(hydroxyphenyl) alkanes or phenol-formaldehyde resins.

The proportions of the components (i) and (ii) in the subjectcompositions may vary over wide limits as a function of the ultimateproperties desired in each particular case. Thus, the weight of theprepolymer (i) may range from 5 to 95%, and advantageously from 20 to80%, of the overall mixture (prepolymer+epoxy resin).

The compositions according to the invention are prepared by simplyintimately admixing the several components. The mixture of the resin andthe prepolymer is heated to a temperature on the order of 50°-120° C.until a homogeneous initimate admixture is obtained. The compositionsmay then be hardened, or cured, at a temperature on the order of 120° C.to 280° C., and preferably from 150° C. to 200° C.

Suitable hardening or curing agents (iii), whether added at the time offormulation of the components (i) and (ii), or subsequently addedthereto at the time of intended use, are the conventional acid or basichardeners of the type typically employed for the curing of the epoxyresins, such as Lewis bases, aliphatic or aromatic primary, secondaryand tertiary amines, Lewis acids, carboxylic acid anhydrides, and thelike.

In a preferred embodiment of the invention, the prepolymer may beprepared in situ by heating a mixture of the epoxy resin, the bis-imideand the N-vinyl-2-pyrrolidone, optionally including the unsaturatedpolyester, at a temperature within the range of 50°-130° C.

The composition of the invention are useful for both molding andimpregnation operations. Same may be employed for the production ofcoatings, adhesive bonding, foams, laminations and reinforced compositematerials. The reinforcing material may be in the form of powders,corrugated or non-corrugated sheets, uni-directional elements or cutnatural or synthetic fibers, such as glass filaments and fibers, boronfibers and filaments, carbon, tungsten, silicon fibers, or fibers ofaromatic polyamide-imides or polyamides. The compositions are ofparticular interest for the production of intermediate articlespre-impregnated without solvent. The impregnation of fibrous substratesmay be effected utilizing conventional techniques, such as immersion ortransfer impregnation. The transferable film and the pre-impregnatedarticles may be directly used, or same may be stored for later use; theyretain their properties to a remarkable degree during storage at ambienttemperature. Composite materials resulting from molding and hardeninghave favorable mechanical properties, particularly concerning bendingstrengths and shear strengths at elevated temperatures. Because of theseproperties, the compositions according to the invention are particularlysuitable for the manufacture of parts for the aeronautical industry.

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative.

EXAMPLE 1

A prepolymer was prepared by mixing, at 120° C., 75 parts (by weight) ofN,N',4,4'-diphenylmethane bis-maleimide, 12.5 parts ofN-vinyl-2-pyrrolidone and 12.5 parts of a solution comprising 40% byweight of allyl phthalate and 60% of an unsaturated polyester having amolecular weight of 2000, obtained by polycondensation of maleic acid,propylene glycol and ethylene glycol. The mixture was placed for 30minutes in an oven heated to 140° C. to obtain a product having asoftening point of 70° C.

The following ingredients were mixed at 90° C.

(a) 100 g epoxy resin of bisphenol A, commercially available under thetrademark "Cy 205";

(b) 100 g of the prepolymer prepared as described hereinabove.

Three grams of a BF₃ /amine (HT 973) hardener were then added thereto.

The homogeneous admixture was degassed under vacuum at 90° C. The timeof gelification at 180° C. was 8 minutes.

A laminate was prepared utilizing the aforedescribed composition. Thecomposition was deposited by coating with a coating blade, at a rate of200 g/m², on silicone coated paper. The film had good adhesion atambient temperature and displayed no voids. This film was used toimpregnate a sheet of unidirectional carbon fibers (AXT 10,000 ofSEROFIM) at a temperature of 70° C. under a pressure of 0.5 bar for 30seconds. The air retained by the carbon fibers was then eliminated bypassing the sheet under vacuum at 70° C. for 15 minutes. 10 plies ofthis pre-impregnated graphite sheet were placed in a mold preheated to80° C. The mold was progressively closed to expel the excess resin, withthe pressure attaining 5 bars at the completion of closing. Thecross-linkable laminate contained 100 g resin per 100 g of the fibers.The assembly was then exposed to a heat treatment for 1 hour at 140° C.and 5 hours at 200° C. The properties of the composite materials were asfollows:

    ______________________________________                                        [1] Density                   1.53                                            [2] Flexural strength (ASTM Standard D 790)                                       at 20° C.          130 kg/mm.sup.2                                 [3] Flexural modulus (ASTM D Standard 790)                                        at 20° C.          9100 kg/mm.sup.2                                [4] Shear strength                                                                at 20° C.          6.7 kg/mm.sup.2                                     at 150° C.         4 kg/mm.sup.2                                   ______________________________________                                    

(shear tests were effected with a distance between supports of 10 mm, atest velocity of 1 mm per minute with 12×2 mm specimens.

EXAMPLE 2

A composite material was prepared by the method described in Example 1.

The following composition was utilized:

    ______________________________________                                        (a)      Novolac epoxy resin (DEN 431)                                                                       58 g                                           (b)      Prepolymer (Example 1)                                                                              42 g                                           (c)      Hardener HT 973       1.5 g                                          ______________________________________                                    

The gelification time of this composition was 24 minutes at 150° C. Thecarbon fibers were impregnated by film transfer and a laminate wasformed by folding 10 piles of the pre-impregnated sheet into a coldmold. The assembly was heated to 130° C. The mold was then closed, thepressure progressively rising from 0.2 to 5 bars at the completion ofthe closure. The laminate contained 60% resin by volume. The assemblywas then heated for one hour at 150° C., 3 hours at 180° C. and 20 hoursat 200° C. The properties of the composite material were as follows:

    ______________________________________                                        [1]     flexural strength (kg/mm.sup.2)                                               at 20° C.  143                                                 [2]     flexural strength                                                             at 120° C. 120                                                 [3]     flexural modulus (kg/mm.sup.2):                                               at 20° C.  10 350                                                      at 120° C. 9 700                                               [4]     Shear strength (kg/mm.sup.2):                                                 at 20° C.  8                                                           at 180° C. 3.4                                                 ______________________________________                                    

EXAMPLE 3

Into a reactor equipped with an agitator and placed into a 110° C.thermostat bath, 10 g of the prepolymer described in Example 1 and 90 gof an epoxy resin consisting of a polyglycidyl ether of aphenol-formaldehyde novolac having a weight in epoxy equivalents ofapproximately 175. The mixture was melted and agitated for a few minutesuntil a homogeneous solution was obtained. Subsequently, 2.7 g of a BF₃/amine hardener were added. The mixture was agitated for 5 minutes anddegassed by placing the reactor under vacuum for 2 minutes. The resinwas poured into a rectangular mold (120×200×13 mm). The assembly washeated for 2 hours at 110° C. and then for 20 hours at 200° C.

The properties of the molded shaped article are compiled in Table 1. Theinitial flexural strength (Rf) and the initial flexural modulus (Mf)were determined at 20° C. and at 120° C.

EXAMPLE 4

The operation described in Example 3 was repeated, but by using amixture of 90 g of the same imide prepolymer, 10 g of the same epoxyresin and 0.35 g of the hardener. The molded shaped article was curedfor 2 hours at 150° C. and then for 20 hours at 200° C.

The properties of the molded shaped article are compiled in Table 1.

EXAMPLE 5

The operation described in Example 3 was repeated by using 42 g of thesame imide prepolymer, 58 g of the same epoxy resin and 1.75 g of thehardener.

The properties of the molded shaped article prepared under theconditions described in Example 4 are compiled in Table 1.

EXAMPLE 6

A prepolymer was prepared by mixing, at 120° C., 80 parts (by weight) ofN-N',4,4'-diphenylmethane bis-maleimide and 20 parts ofN-vinyl-2-pyrrolidone. Following agitation for 30 minutes at thistemperature, a prepolymer, having a viscosity in the molten state of 200mPa.s at 110° C., was obtained.

Example 3 was repeated by using 10 g of the prepolymer thus prepared and90 g of the same epoxy novolac resin; then, after homogenization, 2.7 ofthe BF₃ /amine hardener, were added.

The properties of the molded shaped article prepared under theconditions described in Example 3 are compiled in Table 1.

                  TABLE 1                                                         ______________________________________                                        Properties                                                                              Ex. 3    Ex. 4   Ex. 5  Ex. 6 Ex. 7                                 ______________________________________                                        Rf (kg/mm.sup.2)                                                                at 20° C.                                                                      8.5      7.5     9.6    8.4   8.8                                     at 120° C.                                                                     5.7      5.3     6.8    6     6                                     Mf (kg/mm.sup.2)                                                                at 20° C.                                                                      289      407     338    310   350                                     at 120° C.                                                                     175      225     180    170   218                                   ______________________________________                                    

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, ommission, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims.

What is claimed is:
 1. A composition of matter comprising (i) aprepolymer consisting essentially of a reaction product obtained byreacting (a) a polyimide having the structural formula: ##STR6## whereinD is selected from the group consisting of ##STR7## wherein Y isselected from the group consisting of H, CH₃, and Cl, m is 0, 1 or 2, Ris an organic radical of valency n, containing from 2 to 50 carbonatoms, and n is a number having an average value between 2 and 5, (b)n-vinyl-2-pyrrolidone and (c) an unsaturated polyester which comprises apolycondensate of at least one polycarboxylic acid or ester-formingderivative thereof and at least one polyol, or a solution of such apolycondensate in a polymerizable olefinically unsaturated monomer; and(ii) an epoxy resin comprising a plurality of ##STR8## groups.
 2. Thecomposition of matter as defined by claim 1 further comprising (iii) ahardening agent for the epoxy resin.
 3. The composition of matter asdefined by claim 2 wherein the prepolymer (i) comprises from 5 to 95% byweight of the total amount of prepolymer (i) and epoxy resin (ii). 4.The composition of matter as defined by claim 3, wherein the prepolymer(i) comprises from 20 to 80% by weight of the total amount of prepolymer(i) and epoxy resin (ii).
 5. The composition of matter as defined byclaim 1 or 3, said prepolymer (i) being the product of reaction amongthe polyimide (a), the N-vinyl-2-pyrrolidone (b) and the unsaturatedpolyester (c) in solution in a polymerizable olefinically unsaturatedmonomer.
 6. The composition of matter as defined by claim 3, wherein thepolyimide (a) has the structural formula: ##STR9## wherein L is adivalent radical selected from the group consisting of cyclohexylene,phenylene and radicals having the structural formula: ##STR10## whereinT is selected from the group consisting of --CH₂ --, --C(CH₃)₂ --, --O--and --SO₂ --.
 7. The composition of matter as defined by claim 6,wherein the polyimide (a) is N,N',4,4'-diphenylmethane-bis-maleimide. 8.The composition of matter as defined by claim 6, further comprising areinforcing amount of a filler.
 9. The composition of matter as definedby claim 6, wherein the epoxy resin (ii) is the glycidyl ethers of apoly(hydroxy-phenyl)alkane or a phenol-formaldehyde resin.
 10. Thecomposition of matter as defined by claim 2 in hardened state.
 11. Ashaped article comprising the composition of matter as defined by claim2.
 12. A shaped article comprising the composition of matter as definedby claim
 10. 13. A fibrous substrate impregnated with a composition ofmatter as defined by claim
 2. 14. The composition of matter as definedby claim 2 wherein said hardening agent comprises BF₃.